PREPARATION OF POLY(ETHER-ESTERS) FROM TETRAHYDROFURANS AND POLYCARBOXYLIC ACIDS

Abstract: Poly(ether-esters) can be made from tetrahydrofurans and polycarboxylic acids by using metal perfluoroalkylsulfonates as catalysts. Polymers, some of which are novel, useful as thermoplastic elastomers, spandex fibers or urethane rubbers can be made by reacting dicarboxylic acids containing functional groups with a tetrahydrofuran, especially tetrahydrofuran itself.

Description: TITLE PREPARATION OF POLY(ETHER-ESTERS) FROM TETRAHYDROFURANS AND POLYCARBOXYLIC ACIDS FIELD OF THE INVENTION This invention concerns the preparation of poly(ether-esters) by polymerization of tetrahydrofurans and polycarboxylic acids catalyzed by metal perfluoro- alkylsulfonate catalysts. The resulting products, particularly those made from dicarboxylic acids containing other functional groups, are useful as thermoplastic elastomers, urethane rubbers and spandex fibers. BACKGROUND OF THE INVENTION Polymers, particularly block copolymers, of polytetrahydrofurans (usually as the diols) and polyesters or poly(urea-urethanes) are commonly used in commercial products, such as thermoplastic elastomers (Hytrel® thermoplastic elastomer) , spandex fibers (Lycra® spandex fiber) and urethane rubbers (Adiprene® urethane rubber) . The usual procedure in making these products is to combine a polyether diol with suitable reactants, such as ester segment forming compounds, or urea and/or urethane forming compounds such as amines and/or diols with diisocyanates. Improved methods of making such commercially important polymers are sought by the artisan. U.S. Patent 3,842,019 describes the polymerization of oxiranes and other small ring compounds by a presumed cationic mechanism, using as the catalyst the decomposition products of metal perfluoroalkyl¬ sulfonates. These catalysts are described as "latent", that is no reaction occurs until the metal salt is decomposed. The reactions reported are relatively slow, even at elevated temperatures. U.S. Patents 5,084,586 and 5,124,417 describe the cationic polymerization of various monomers, including cyclic ethers, using onium cations, whose corresponding anions are fluororalkylsulfatometallates. Onium ion catalyzed cationic polymerizations are well known, and there is no mention in these patents of the use of metal salts not containing onium ions, such as metal triflates, as catalysts for the polymerization of cyclic ethers. Japanese Patent Application 51-82397 describes the polymerization of tetrahydrofuran using a combination of fluorosulfonic acid and a carboxylic acid as catalysts. No mention is made of metal salts, such as metal triflates as catalysts. J. S. Hrkach, et al., Macromolecules, vol. 23, p. 4042-4046 (1990) describe the polymerization of tetrahydrofuran using trimethylsilyl trifluoromethane- sulfonate as the initiator. No mention is made of any other triflates as catalysts for this polymerization. G. A. Olah, et al., J. Appl. Polym. Sci., Vol. 45, 1355-1360 (1992) describe the use of boron, aluminum and gallium tristriflate to catalyze the polymerization of THF. SUMMARY OF THE INVENTION This invention concerns a process for the production of poly(ether-esters) , comprising, contacting a tetrahydrofuran with a polycarboxylic acid of the formula A(Cθ 2 H) x and a catalyst of the formula MZ s # Q t , wherein: M is a metal selected from the group consisting of cobalt, tungsten, vanadium, niobium, strontium, barium, scandium, yttrium, the rare earth metals, titanium, zirconium, hafnium, chromium, molybdenum, tantalum, rhenium, iron, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver. gold, zinc, cadmium, mercury, aluminum, gallium, indium, thulium, germanium, tin, lead, arsenic, antimony and bismuth; Z is an anion of the formula "OSO 2 R 5 , wherein R 5 is perfluoroalkyl containing 1 to 12 carbon atoms or part of a fluorinated group wherein the carbon atoms alpha and beta to the sulfonate group are together bonded to at least four fluorine atoms; s is 1 when M is silver; s is 2 when M is strontium, barium, cobalt, rhodium, iridium, palladium, platinum, chromium, zinc, cadmium or mercury; s is 3 when M is scandium, yttrium, a rare earth metal, arsenic, antimony, bismuth, gold, iron, ruthenium, osmium, aluminum, gallium, indium or thulium; s is 4 when M is titanium, zirconium, hafnium, molybdenum, germanium, tin, or lead; s is 5 when M is rhenium, vanadium, niobium or tantalum; s is 6 when M is tungsten; Q is a neutral ligand; t is 0 or an integer of 1 to 6; and each A is independently an organic radical having x free valencies; each x is independently 2, 3, 4, 5 or 6; and provided that: A is bound to carboxyl groups through a carbon atom; said polycarboxylic acid has a pKa of about 6 or less; said polycarboxylic acid does not by itself catalyze polymerization of the tetrahydrofuran; and the ratio of equivalents of carboxyl groups of said polycarboxylic acid to moles of said catalyst is less than 6. This invention also concerns a polymer consisting essentially of a repeat unit of the formula [ (-CHR 1 CR 2 R 3 CR 2 R 3 CHR 4 0-) n C(0)AC(0)O-] wherein: each R 1 , R 2 , R 3 and R 4 is hydrogen or hydrocarbyl containing 1 to 20 carbon atoms; each n is independently an integer of 1 or more; each A is independently hydrocarbylene or substituted hydrocarbylene containing one or more functional groups selected from the group consisting of imide, amide, urea and urethane; and provided that each A is bound to a ester group through a carbon atom. DETAILS OF THE INVENTION In the instant process a tetrahydrofuran is copolymerized with a polycarboxylic acid to yield a poly(ether-ester) . By a tetrahydrofuran (THF) is meant the common meaning, a compound containing a saturated five membered ring in which one of the ring atoms is oxygen and the other four ring atoms are carbon. Preferred tetrahydrofurans have the formula I I wherein each R 1 , R 2 , R 3 and R 4 is independently hydrogen or hydrocarbyl containing 1 to 20 carbon atoms. In especially preferred THFs, R 1 , one of R 2 and all of R 3 and R 4 are hydrogen, and the remaining R 2 is alkyl containing 1-4 carbon atoms, particularly the remaining R 2 is methyl. In another especially preferred embodiment all of R 1 , R 2 , R 3 and R 4 are hydrogen. A tetrahydrofuran is copolymerized with a polycarboxylic acid of the formula A(Cθ2H) x , wherein A is an organic radical, and wherein A is bound to each carboxyl group through a carbon atom. By "through a carbon atom" is meant that each carboxyl group is bound to a carbon atom which is part of A. A may contain any substituent which does not react during, or disturb, the polymerization. Suitable functional groups include halo, ester, amide, urethane, urea, keto, ether, imide, and sulfone, and hydrocarbon based "functional groups" such as olefins, aromatic rings, and acetylenic bonds. Especially preferred functional groups are ester, amide, imide, urethane and urea. The functional groups should be picked so that they don't undergo an acid base reaction with the carboxyl groups of the polycarboxylic acid. Thus aliphatic amine groups should not be present and are classified as among those groups which interfere with the polymerization. Useful polycarboxylic acids include, but are not limited to, maleic acid, fumaric acid, succinic acid, adipic acid, isophthalic acid, terephthalic acid, and 1,2,4-benzenetricarboxylic acid. Preferred carboxylic acids are adipic, isophthalic and terephthalic acids. The polycarboxylic acid has a pKa of less than 6, preferably less than 5, and should not by itself catalyze the polymerization of the tetrahydrofuran. In preferred carboxylic acids, x is 2 (a dicarboxylic acid) . When x is more than two, a branched and/or crosslinked poly(ether-ester) will be produced. The catalyst may be a yttrium or rare earth compound of the formula MZ 3 where M is a trivalent ion of yttrium, or one of the rare earths, lanthanum, cerium, praeseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Preferred metals, M, are strontium, scandium yttrium, the rare earth metals, titanium, zirconium. hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, rhenium, iron, ruthenium, palladium, copper, gold, zinc, tin and bismuth. More preferred metals are yttrium, the rare earth metals, and scandium. Especially preferred metals are yttrium, ytterbium, dysprosium, erbium, neodymium, lanthanum, and scandium. Another preferred metal is "mischmetall" (sometimes also called "didymium"), which is a mixture of rare earth metals as obtained from the ore. It is believed monovalent anions that are relatively nonnucleophilic are useful as Z. Examples of such anions are tetraphenylborate, -OSO 2 R 5 , wherein R 5 is perfluoroalkyl, or wherein R 5 is part of a fluorinated polymer wherein the carbon atoms alpha and beta to a sulfonate group are together bonded to at least 4 fluorine atoms (as in -CF 2 CF 2 OSO 2 -) . It is preferred if R 5 is perfluoroalkyl. In a particularly preferred R 5 is trifluoromethyl, and that anion is herein called "triflate". Generally speaking, any metallic compound in which the correct metal in the correct oxidation state (see above) is present and bonded to a triflate or a similar anion will be a catalyst. Such a compound must of course be reasonably stable during the polymerization or decompose to another compound which is still a triflate (or similar anion) compound of the metal in the correct oxidation state. The metal catalysts may optionally contain one or more neutral ligands, Q, coordinated to the metal. By a neutral ligand is meant a neutral compound that can coordinate with the catalysts, usually the metal cation. Neutral ligands include water, and ethers such as dimethyl ether and tetrahydrofuran. Useful compounds containing neutral ligands include bis(n-cyclopenta- dienyl)tetrahydrofuran-bis(trifluoromethanesulfonate)- zirconium and bis(n-cyclopentadienyl)tetrahydrofuran- bis(trifluoromethanesulfonate)hafnium. In general, the higher the molar ratio of metal compound to cyclic ether monomer originally present, the lower the molecular weight of the resulting polyether will be. The polymerization may be run at a temperature of about -80°C to about 130°C. If this temperature is above the boiling point of the cyclic ether monomer, a pressure vessel may be used. A preferred temperature is ambient to the boiling point of the monomer, or 110°C, whichever is lower. An inert solvent such as di-n-butyl ether, diethyl ether or toluene may be used, but it is preferred if solvents are not present. Protic compounds such as water, methanol and ethanol should preferably not be present, and it is convenient to exclude them by drying the starting materials and keeping the process under an inert dry gas such as nitrogen. As in most chemical processes, the ingredients should be mixed at least initially. Continued agitation is preferred to assure that the process materials remain well mixed, and to avoid overheating. The polymerization is mildly exothermic. If the polymerization temperature goes up appreciably, refluxing of the monomer may be used to help cool the process. The molar ratio of THF to polycarboxylic acid at the beginning of the polymerization can be about 0.2 to about 60, preferably about 2 to about 15. Generally speaking, the higher the relative molar amount of polycarboxylic acid present, the greater the incorporation (per THF unit) of ester units (from polycarboxylic acid) will be. The desired amount of ester present will depend on the polycarboxylic acid used, and the use of the polymeric product. However, the ratio of equivalents of carboxylic acid groups (in the polycarboxylic acid) to the number of moles of catalyst (MZ s « Qt) should be less than six (i.e., carboxyl present/moles catalyst <6) . In a simple batch reaction this means this ratio will be less than 6 at the start of the polymerization, and decrease as the polycarboxylic acid is polymerized, and its carboxyl groups are "used up" and converted to ester groups. However, as the carboxyl groups are used up by polymerization, they may be replaced by the addition of polycarboxylic acid, so long as the above ratio is less than 6. When a dicarboxylic acid (x=2) is used in the polymerization, a (product) polymer repeat unit can be represented by the general formula [(-CHR 1 CR 2 R 3 CR 2 R 3 CHR 4 0-) n C(0)AC(0)0-] wherein all of the symbols have the definitions as given above, and n is an integer of 1 or more. In preferred polymers, n is about 5 to about 500, more preferably about 8 to about 100. Useful A groups include tetramethylene, p-phenylene, and m-phenylene. In another preferred polymer, n is 5 or more, more preferably 10 or more. It is preferred if A contains urea or urethane groups. By a urea group is meant -NH-C(0)-NR 10 -, and by a urethane group is meant -0-C(0)-NH-, wherein R 10 is hydrogen or hydrocarbyl containing 1 to 20 carbon atoms. It is preferred if R 10 is hydrogen. In other preferred polymers, all of R 1 , R 2 , R 3 and R 4 are hydrogen, or one of R 2 is methyl, the other R 2 is hydrogen, and all of R 1 , R 3 , and R 4 are hydrogen. A preferred polymer is one in which A has the formula -R 6 -E-C(0)-NH-R 7 -NH-C(0)-E-[-R 8 -E-C(0)-NH-R 7 -NH-C(0)-E-] m -R 6 - wherein each R 6 , R 7 and R 8 is independently hydrocarbylene or substituted hydrocarbylene containing 2 to 25 carbon atoms, E is -0-or -NR 10 -, wherein R 10 is as defined above, and m is an average of 0 to 10. Such polymers are made from dicarboxylic acids A(Cθ 2 H) x , wherein x is 2, and A has the formula shown above. Such diacids can be made by the reaction of one or more diisocyanates with one or more aminocarboxylic acids, hydroxy carboxylic acids, diamines, aminoalcohols and diols. The group R 6 is derived from the amino- or hydroxycarboxylic acid, R 7 is derived from an organic diisocyanate, and R 8 is derived from a diamine or diol. When a particular E is -0-, it can be derived from the reaction of an isocyanate group and a hydroxy group to form a urethane. When a particular E is -NR 10 -, it can be derived from the reaction of an isocyanate and a primary amino group when R 10 is hydrogen, and a secondary amino group when R 10 is hydrocarbyl, to form a urea. All preferred formulas for dicarboxylic acids also refer to "A" in the polymer. Dicarboxylic acids containing various functional groups can be made by methods known in this art. See, for instance, Chem. Abs., Vol. 44, 51 04 b-d (1950), S. Hsiao, et al., J. Polym. Sci., Part A, Vol. 28, pp. 2169-2178 (1990), and R. E. Asay et al., J. Heterocyclic Chem., Vol. 14, pp. 85-90 (1977). To give a concrete example, if it is desired to make the dicarboxylic acid wherein both of R 6 are 1,4- phenylene, R 7 is R 8 is 1,4-phenylene, every E is -NH-, and m is an average of 1, one could react (preferably in solution) one mole of p-phenylene diamine, two moles of p-amino- benzoic acid, and two moles of bis(4-isocyanato- phenyl)methane. To prepare the corresponding polymer where every E is -0-, one would use hydroquinone and p- hydroxybenzoic acid in place of p-phenylenediamine and p-aminobenzoic acid, respectively. To vary m, the ratio of diamine, diol and/or aminomonool to aminocarboxylic acid and/or hydroxyacid would be varied. The amount of diisocyanate would also be changed so it could react with all of the amino and/or hydroxy groups present. As the art skilled will understand, in reactions of this type, a distribution of m values will be obtained (except when m is 0) for individual molecules, and overall, m is the arithmetic average of the values for individual molecules. Fractional values of m are possible by varying the stoichiometry. Experiment 1 illustrates the preparation of such a dicarboxylic acid. In preferred dicarboxylic acids: R 6 and R 8 are each independently 1,4-phenylene, 1,3-phenylene, and n-alkylene containing 2 to 6 carbon atoms; R 7 is 1,4-phenylene, 1,3-phenylene, n-alkylene containing 2 to 6 carbon atoms, or R 6 and R 8 are each independently 1,4-phenylene, 1,3-phenylene, and n-alkylene containing 2 to 6 carbon atoms; R 7 is ethylene, or In other preferred dicarboxylic acids E is -NR 10 - wherein R 10 is hydrogen, or m is an average of 0 to about 3. By hydrocarbylene herein is meant a divalent radical containing only carbon and hydrogen. A substituted hydrocarbylene is a radical which also contains substituent groups that do not interfere with any of the reactions, including polymerization, described herein. Suitable functional groups have been listed above. In the Examples, the following abbreviations are used: DMAC - N,N-dimethylacetamide MDI - bis(4-isocyanatophenyl)methane RB - round-bottomed The polymeric product of this invention, particularly one made from dicarboxylic acids containing other functional groups, is useful as a thermoplastic elastomer, urethane rubber or in spandex fiber. The ester groups of the poly(ester-ether) may be hydrolyzed to form polyether diols. EXAMPLE 1 Polymerization of THF with Ytterbium Triflate and 3-Methyladipic Acid In a dry box, ytterbium triflate (10.0 g) and 3-methyladipic acid (5.0 g) were added to each of three separate oven dried 100 mL RB flasks equipped with stirring bars. The flasks were sealed with rubber septa and then removed from the dry box. Nitrogen bleeds were attached and THF (20.0 mL) was added to each flask. After 2, 4, and 6 hours a polymerization was terminated via the addition of water (25 mL) , ether (25 mL) and THF (50 mL) . The resulting organic phases were separated, concentrated at reduced pressure and then dried under vacuum. Polymer yields and GPC analysis: Mn Polymerization Time Polymer Yield (g) (PS* STD) Mw PD 2 hrs. 2.96 8630 13800 1.61 4 hrs. 3.15 8170 13300 1.63 6 hrs. 4.79 7230 12600 1.75 *Polystyrene standard EXAMPLE 2 Polymerization of THF with Ytterbium Triflate and Adipic Acid In a dry box, ytterbium triflate (5.0 g) and adipic acid (1.21 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with rubber septum and then removed from the dry box, a nitrogen bleed was attached and THF (20.0 mL) added. After 60 minutes the polymerization was terminated via the addition of water (25 mL) , ether (25 mL) and THF (50 mL) . The resulting organic phase was separated, concentrated at reduced pressure and then dried under vacuum. Polymer yield: 7.65 g. GPC analysis (PS STD.) : Mn = 14000, Mw = 39300, PD = 2.80, IR analysis (CHCI 3 , cm" 1 ): 2860, 1727 (C=0) , 1370, 1100. EXAMPLE 3 Polymerization of THF with Ytterbium Triflate and Maleic Acid In a dry box, ytterbium triflate (5.0 g) and maleic acid (1.9 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with rubber septum and then removed from the dry box, a nitrogen bleed was attached and THF (20.0 mL) added. After 60 minutes the polymerization was terminated via the addition of water (25 mL) , ether (25 mL) and THF (50 mL) . The resulting organic phase was separated, concentrated at reduced pressure and then dried under vacuum. Polymer yield: 3.98 g. GPC analysis (PS STD): Mn = 8950, Mw = 16800, PD = 1.88. EXAMPLE 4 Polymerization of THF with Ytterbium Triflate and Isophthalic Acid In a dry box, ytterbium triflate (5.0 g) and isophthalic acid (2.76 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with rubber septum and then removed from the dry box, a nitrogen bleed was attached and THF (20.0 mL) added. After 60 minutes the polymerization was terminated via the addition of water. The polymer was dissolved in methylene chloride. The resulting organic solution was washed with water (2 x 200 mL) , then concentrated at reduced pressure and then dried under vacuum. Polymer yield: 12.24 g. GPC analysis (PS STD): Mn = 258000, Mw = 559000, PD = 2.16. EXAMPLE 5 Polymerization of THF with Ytterbium Triflate and Terephthalic Acid In a dry box, ytterbium triflate (5.0 g) and terephthalic acid (2.76 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with rubber septum and then removed from the dry box, a nitrogen bleed was attached and THF (20.0 mL) was added. After 60 minutes the polymerization was terminated via the addition of water. The polymer was dissolved in methylene chloride. The resulting organic solution was washed with water (2 x 200 mL) , then concentrated at reduced pressure and then dried under vacuum. Polymer yield: 3.66 g. GPC analysis (PS STD): Mn = 308000, Mw = 744000, PD = 2.42. EXAMPLE 6 Polymerization of THF with Ytterbium Triflate and A In a dry box, ytterbium triflate (5.0 g) and A (1.5 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with rubber septum and then removed from the dry box, a nitrogen bleed was attached and THF (20.0 mL) added. After 120 minutes the polymerization was terminated via the addition of water, THF and ether. The resulting separated organic solution was washed with sodium bicarbonate (2 x 25 mL) , then concentrated at reduced pressure and dried under vacuum. Polymer yield: 2.37 g. EXAMPLE 7 Polymerization of THF with Ytterbium Triflate and A In a dry box, ytterbium triflate (5.0 g) and A (0.5 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with rubber septum and then removed from the dry box, a nitrogen bleed was attached and THF (20.0 mL) was added. After 60 minutes the polymerization was terminated via the addition of water, THF and ether. The resulting separated organic solution was washed with sodium bicarbonate (2 x 25 mL) , then concentrated at reduced pressure and then dried under vacuum. Polymer yield: 1.97 g. GPC analysis (PS STD): Mn = 72200, Mw = 173000, PD = 2.39. EXAMPLE 8 Polymerization of THF with Ytterbium Triflate and B In a dry box, ytterbium triflate (5.0 g) and B (1.5 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with rubber septum and then removed from the dry box, a nitrogen bleed was attached and THF (20.0 mL) added. After 120 minutes the polymerization was terminated via the addition of water, THF and ether. The resulting separated organic solution was washed with sodium bicarbonate (2 x 25 mL) , then concentrated at reduced pressure and then dried under vacuum. Polymer yield: 8.49 g. GPC analysis (PS STD): Mn = 127000, Mw = 341000, PD = 2.67. EXAMPLE 9 Polymerization of THF with Ytterbium Triflate and 1.2.4-Benzenetricarboxvlic-- Acid In a dry box, ytterbium triflate (5.0 g) and 1,2,4-benzenetricarboxylic acid (2.0 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with rubber septum and then removed from the dry box, a nitrogen bleed was attached and THF (20.0 mL) added. After 21 hours the polymerization was terminated via the addition of water, THF and ether. The resulting separated organic solution was washed with sodium bicarbonate (25 mL) upon which a gelatinous material resulted. HC1 was then added and the organic phase separated, then concentrated at reduced pressure and finally dried under vacuum. Polymer yield: 8.91 g. GPC analysis (PS STD) : Mn = 100000, Mw = 227000, PD = 2.26. EXAMPLE 10 Polymerization of THF with Ytterbium Triflate and l.l'-Ethylenebis(5-oxo-3-pyrrolidecarboxylic Acid) In a dry box, ytterbium triflate (5.0 g) and 1,1'-ethylenebis (5-oxo-3-pyrrolidecarboxylic acid) (1.0 g) were added to an oven dried 100 L RB flask equipped with a stirring bar. The flask was sealed with rubber septum and then removed from the dry box, a nitrogen bleed was attached and THF (20.0 mL) added. After 3 hours the polymerization was terminated via the addition of water, THF and ether. The resulting separated organic solution was washed with sodium bicarbonate then the organic phase separated, concentrated at reduced pressure and finally dried under vacuum. Polymer yield: 5.21 g. GPC analysis (PS STD) : Mn = 73200, Mw = 194000, PD = 2.65. EXAMPLE 11 Polymerization of THF with Ytterbium Triflate and Isophthalic Acid and Terephthalic Acid In a dry box, ytterbium triflate (5.0 g) , terephthalic acid (2.00 g) and isophthalic acid (0.5 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with rubber septum and then removed from the dry box, a nitrogen bleed was attached and THF (20.0 mL) added. After stirring overnight the polymerization was terminated via the addition of water. The polymer was dissolved in methylene chloride. The resulting organic solution was washed with water (2 x 200 mL) , then concentrated at reduced pressure and then dried under vacuum. Polymer yield: 7.38 g. GPC analysis (PS STD): Mn = 42000, Mw = 138000, PD = 3.30. EXAMPLE 12 Polymerization of THF with Ytterbium Tr flate and N-Acetyl-L-σlutamic Acid In a dry box, ytterbium triflate (15.0 g) and N-acetyl-L-glutamic acid (1.0 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with rubber septum and then removed from the dry box, a nitrogen bleed was attached and THF (20.0 mL) added. After stirring overnight the polymerization was terminated via the addition of water, THF and ether. The resulting organic solution was washed with water, then concentrated at reduced pressure and then dried under vacuum. Polymer yield: 2.82 g. GPC analysis (PS STD) : Mn = 16600, Mw = 80500, PD = 4.83. EXPERIMENT 1 Preparation of (HOCOPh-NHC(0)NH-Ph) 2 -CH 2 In a dry box, MDI (25.0 g) was weighed into a 500 mL RB flask equipped with a stirrer, dimethylacet- amide (DMAC, 75 mL) was then added. A solution of 4- aminobenzoic acid (27.8 g) in DMAC (25 mL) was slowly added to the stirred MDI/DMAC solution. The reaction was allowed to stir overnight, then the reaction mixture was poured into diethyl ether. The resulting precipitate was filtered and dried under vacuum at 100°C. In this compound all phenyl rings are para substituted. EXAMPLE 13 Polymerization of THF with (Hθ2CPh-NHC(0)NH-Ph) 2 -CH 2 and Ytterbium Triflate In a dry box, ytterbium triflate (5.00 g) and (H0 2 OPh-NHC(0)NH-Ph) 2 -CH 2 (1.0 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with a rubber septum and removed from the dry box. After the attachment of a nitrogen bleed THF (20.00 mL) was added via syringe. After 18 hrs. the resulting solid mass was dissolved in THF (~800 mL) and water (~10 mL) . The resulting mixture was filtered through Celite and then concentrated at reduced pressure to ~200 mL, then poured into a Waring blender containing water (~500 mL) . The resulting precipitated polymer was recovered via filtration and dried under vacuum affording 10.30 g of white material. EXAMPLE 14 Polymerization of THF/3-Me-THF with (Hθ 2 CPh-NHC(0)NH-Ph) 2 ~CH 2 and Ytterbium Triflate In a dry box, ytterbium triflate (5.00 g) and (H0 2 CPh-NHC(0)NH-Ph) 2 -CH 2 (1.0 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with a rubber septum and removed from the dry box. After the attachment of a nitrogen bleed THF (15.00 mL) and 3-Me-THF (5.0 mL) were added via syringe. After 18 hrs. the resulting solid mass was dissolved in THF (-800 mL) and water (-10 mL) . The resulting mixture was filtered through Celite and then concentrated at reduced pressure to -200 mL, then poured into a Waring blender containing water (-500 mL) . The resulting precipitated polymer was recovered via filtration and dried under vacuum affording 7.38 g of white material. EXPERIMENT 2 Preparation of (HO 2 CC(CH 3 ) 2 CH 2 O-C(0)NH-Ph) 2 ~CH 2 In a dry box, MDI (25.0 g) was weighed into a 500 mL RB flask equipped with a stirrer, dimethylacet- amide (DMAC, 70 mL) was then added followed by hydroxypivalic acid (23.8 g) . The reaction was allowed to stir overnight, then the reaction mixture was poured into water. The resulting precipitate was filtered and dried under vacuum at 100°C, affording 46.28 g (94.84%) of product. All phenyl rings in this compound are para substituted. EXAMPLE 15 Polymerization of THF with (Hθ2CC(CH 3 ) 2 CH 2 θ-C(0)NH-Ph) 2 -CH 2 and Ytterbium Triflate In a dry box, ytterbium triflate (10.00 g) and (H0 2 CC(CH 3 ) 2 CH 2 θ-C(0)NH-Ph) 2 -CH 2 (1.0 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with a rubber septum and removed from the dry box. After the attachment of a nitrogen bleed THF (20.00 mL) was added via syringe. After 16 hrs. the resulting solid mass was repeatedly washed with water, then dried under vacuum affording 6.40 g of white material. NMR and GPC analysis showed the product to be contaminated with a small amount of the starting diacid.

Claims: What is claimed is: 1. A polymer consisting essentially of a repeat unit of the formula [ (-CHR 1 CR 2 R 3 CR 2 R 3 CHR 4 0-) n C(0)AC(0)0-] wherein: each R 1 , R 2 , R 3 and R 4 is hydrogen or hydro¬ carbyl containing 1 to 20 carbon atoms; each n is independently an integer of 1 or more; each A is independently hydrocarbylene or substituted hydrocarbylene containing one or more functional groups selected from the group consisting of imide, amide, urea and urethane; and provided that each A is bound to an ester group through a carbon atom. 2. The polymer as recited in Claim 1 wherein A is hydrocarbylene and said functional groups are urea, urethane, or urethane and urea. 3. The polymer as recited in Claim 2 wherein A is -R 6 -E-C(0)-NH-R 7 -NH-C(0)-E-[-R 8 -E-C(0)-NH-R 7 -NH-C(0)-E-] m -R 6 - wherein each R 6 , R 7 and R 8 is independently hydrocarbylene containing 2 to 25 carbon atoms, E is -0- or -NR 10 -, R 10 is hydrogen or hydrocarbyl containing 1 to 20 carbon atoms, and m is an average of 0 to 10. 4. The polymer as recited in Claim 1 wherein all of R 1 , R 2 , R 3 and R 4 are hydrogen; or one of R 2 is methyl, the other R 2 is hydrogen, and all of R 1 , R 3 , and R 4 are hydrogen. 5. The polymer as recited in Claim 3 wherein R 10 is hydrogen and: all of R 1 , R 2 , R 3 and R 4 are hydrogen; or one of R 2 is methyl, the other R 2 is hydrogen, and all of R 1 , R 3 , and R 4 are hydrogen. 6. The polymer as recited in Claim 3 wherein n is an average of about 8 to about 100. 7. The polymer as recited in Claim 3 wherein: R 6 and R 8 are each independently 1,4-phenylene, 1,3-phenylene, or n-alkylene containing 2 to 6 carbon atoms; and R 7 is 1,4-phenylene, 1,3-phenylene, n-alkylene containing 2 to 6 carbon atoms, or 8. The polymer—as recited ® in Claim.3 wherein: R 6 and R 8 are each independently 1,4-phenylene, 1,3-phenylene, and n-alkylene containing 2 to 6 carbon atoms; and R 7 is ethylene or 9. The polymer as recited in Claim 5 wherein: R 6 and R 8 are each independently 1,4-phenylene, 1,3-phenylene, or n-alkylene containing 2 to 6 carbon atoms; R 7 is 1,4-phenylene, 1,3-phenylene, n-alkylene containing 2 to 6 carbon atoms, or 10. The polymer as recited in Claim 3 wherein E is -NR 10 -, and R 10 is hydrogen. 11. The polymer as recited in Claim 3 wherein m is an average of 0 to about 3. 12. A process for the production of poly(ether- esters) , comprising, contacting a tetrahydrofuran with a polycarboxylic acid of the formula A(Cθ 2 H) x and a catalyst of the formula MZ s «Q t , wherein: M is a metal selected from the group consisting of cobalt, tungsten, vanadium, niobium, strontium, barium, scandium, yttrium, the rare earth metals, titanium, zirconium, hafnium, chromium, molybdenum, tantalum, rhenium, iron, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, aluminum, gallium, indium, thulium, germanium, tin, lead, arsenic, antimony and bismuth; Z is an anion of the formula "OS0 2 R 5 , wherein R 5 is perfluoroalkyl containing 1 to 12 carbon atoms or part of a fluorinated group wherein the carbon atoms alpha and beta to the sulfonate group are together bonded to at least four fluorine atoms; s is 1 when M is silver; s is 2 when M is strontium, barium, cobalt, rhodium, iridium, palladium, platinum, chromium, zinc, cadmium or mercury; s is 3 when M is scandium, yttrium, a rare earth metal, arsenic, antimony, bismuth. gold, iron, ruthenium, osmium, aluminum, gallium, indium or thulium; s is 4 when M is titanium, zirconium, hafnium, molybdenum, germanium, tin, or lead; s is 5 when M is rhenium, vanadium, niobium or tantalum; s is 6 when M is tungsten; Q is a neutral ligand; t is 0 or an integer of 1 to 6; and each A is independently an organic radical having x free valencies; each x is independently 2, 3, 4, 5 or 6; and provided that: A is bound to carboxyl groups through a carbon atom; said polycarboxylic acid has a pKa of about 6 or less; said polycarboxylic acid does not by itself catalyze polymerization of the tetrahydrofuran; and the ratio of equivalents of carboxyl groups of said polycarboxylic acid to moles of said catalyst is less than 6. 13. The process of Claim 12 wherein x is 2. 14. The process as recited in Claim 12 wherein M metal selected from the group consisting of strontium, barium, scandium, yttrium, the rare earth metals, titanium, zirconium, hafnium, chromium, molybdenum, tantalum, rhenium, iron, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold, zinc, cadmium, mercury, germanium, tin, lead, arsenic, antimony and bismuth. 15. The process as recited in Claim 12 wherein the tetrahydrofuran is of Formula I, wherein R 1 , R 4 , and all of R 2 and R 3 are hydrogen 16. The process as recited in Claim 15 wherein the tetrahydrofuran is of Formula I, wherein R 1 and R 4 are hydrogen, one of R 2 is hydrogen, the other R 2 is methyl, and both of R 3 are hydrogen 17. The process as recited in Claim 12 wherein R 5 is trifluoromethyl. 18. The process as recited in Claim 12 wherein A is tetramethylene, p-phenylene, or m-phenylene. 19. The process as recited in Claim 12 wherein A contains one or more of imide, ester, amide, urethane or urea. 20. The process as recited in Claim 12 wherein the tetrahydrofuran is of Formula I wherein all of R 1 , R 2 , R 3 and R 4 are independently hydrogen or a Ci to C 20 hydro¬ carbyl.

Inventors: CITRON JOEL DAVID, DRYSDALE NEVILLE EVERTON, CITRON, JOEL, DAVID, DRYSDALE, NEVILLE, EVERTON
Applicants: DU PONT, E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1994
Main classification: C08G63
IPC codes: C08G63, C08G65